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gfiigipgme acorn p 'Q FFlCE' no ct'noce'zris'i a 1 SOLUBILIZED HIGHER ALIPHATIG SUL- PI-IIDES'AND PROCESS FOR THEIR PRO- DUCTION Alfred William Baldwin and Henry Alfred Piggott, Blackley, Manchester, England, assignors to Imperial Chemical Industries Limited, a corporation of GreatBritain N Drawing. Application February 27, 1935,

Serial No. 1934 14 Claims.

This invention relates to the manufacture of new substances having properties that make them valuable as Wetting, cleansing and emulsifying agents. e

5 This invention has as an object the prepara- 8,553. In Great Britain March 12,

invention, use may be made of any aliphatic mercaptan containing a chain of eight or more carbon atoms. As examples of other mercaptan-s which may be used in preparing these new compounds, mention should be made of the octyl, 5 tion of new and useful chemical compounds. A decyl, undecyl, dodecyl, tetradecyl, pentadecyl, er j t resides in d v s ng novel proceoctadecyl, eikesyl, ceryl, melissyl, oleyl, linoleyl, dures whereby these .new chemical compounds erucyl, and ricinoleyl mercaptans. In place of may be obtained. A- still further object lies inthe using any one of the aforementioned mercaptans,

0 use of these new chemical compounds innovel use may be made of desired. mixtures thereof. technical applications. .Other objects will ap- The use of a mixture of octyl, decyl, .dodecyl, pear hereinafter. tetradecyl, and hexadecyl mercaptans is fre These objects a abwm'plished by the. fO quently to be preferred since a cheap mixture s invention where n n w p u ds aving the of these mercaptans is obtained when the mixe a. R?SO4 in W ch A pture of alcohols obtained from the hydrogenation 15 resents an aliphatic group n n a C a of coconut oil is used as raw. material in the of eight or more carbon atoms, R stands for an preparation of th mercaptans, al p a c pr Stands for y gen 01' Those compounds which come Within the a soluble salt-forming g p. In the preferred scope of the present invention and in which R embodiment ofvtheinvention, A stands for an represents an aliphatic hydrocarbon group at-- alkyl group Containing from t to t y tached to an sOiM'group are prepared by a genbon atoms, R. stands fora short chain. (two-t0 eral method which has been illustrated above in S Ca atoms) aliphatic hydrocarbon group, the example. In place of using ethylene chloroand M stands for analkali metal. hydrin to prepare these compounds, it is also The invention is illustrated but not limited by feasible t use a number of other halohmirins, the follow examp in w h the p ts ar by Other halohydrins which may be employedin Weight. the synthesis of some of the new compounds Example comprehended by the present invention are: 10 partsof cetyl mercaptan are dissolved in 70 ethylene bromohydfln pmpylepe bromohydrm parts of methyl alcohol containing 2 parts of glyceryl alpha rimmchmrohyfinm glycerifl beta 30 sodium. methoxide; 3.1 parts of ethylene chloromonochlolqhydrln, glyceryl di-chlorohydrm, the hydrin are then added and the mixture is boiled correspoedmg glycer i 'lthe under arefl ux condenser for 2 hours. It is then dmxy dl'alkyl sulphldes Preparmg the filtered from precipitated sodium chloride. "The compounds of the present mveptlon may be trate is concentrated by evaporation. On 0001- paredby the method Set forth Examples 6 and 35 ing 2-hydroxy-ethy1 cetyl sulphide separat 7 of U. S. Patent No. 1,987,526 in place of follow This may be purified still further, if desired, by the e al procedure given in the example recrystallization froma mixture of acetone and of the Present speclfficatlon The followmghy' 'methyl alcohol, I droxy dl-alkyl sulphides may be sulphatedto ob- I I 0 10 parts of the sulphide so obtained, 7.5 parts tam compound? commg Wlthm h $9 of the 40 of sodium pyrosulphate and 2.7 parts of pyridine prffsent lnventlonl hydroXy-ethyl decyl sulare stirred at 9095 C. until a sample dissolves phlde, zhydroxy'ethyl F Sulphlde? in water to a clear foamingsolution. The reacdroXy-ethyl tetraidecyl sulphlde z'hydroxy7ethyl tion mixture is stirred into 40 parts of water, 10 hexadecyl 'sulphlde g'hydroxy'ethyl P 5 parts of sodium chloride are added and, after sulphide, ydr0Xy propyl dodecyl s p l stirring several hours to complete the precipiy P DY hBXadPCYI Sulphlde, and the tation, the product is filtered off. A white pasty pound made by ne two f cetyl solid is obtained. This dissolves readily in hot Captain th one mol. of glyceryl di-chlorohydrm. water'to yield clear solutions with excellent In p y g ese halohydrinsto prepare the foaming and' detergent properties. If desired the o pounds of e p s mventlon, the synthe- 50 pasty solid may be dried. The. compound may sis is so governed that each of the halogen atoms after drying be freed from inorganic salts by of the halohydrin is replaced by an alky e extraction with methyl alcohol. I y apt-an group, a c of t h droxy roups In place ofusing cetyl mercaptan to prepare of the halohydrin is converted to an OSOaM the new compounds comprehended by thepresent group, ,Inviewof their .cheapness, ethylene co ti F ii N o s.

chlorohydrin and glyceryl alpha mono chlorohydrin are preferred for making compounds such as that given in the example.

In the compounds of the present invention, M

will usually stand for hydrogen or an alkali metal. However, ammonia, methyl amine, butyl amine, cyclohexyl amine, mono-, di-, or tri-.

ethanol amine, piperidine, morpholine, or other water soluble organic bases may be used to neutralize the acid hydrogen of the compounds of the present invention.

Some compounds which may be prepared and which come within the scope of this invention are: sodium dodec'yl mercapto ethyl acid sulphate; sodium tetradecyl mercapto ethyl acid sulphate; sodium hexadecyl, mercapto ethyl acid sulphate; sodium octadecyl mercapto ethyl acid sulphate; sodium dodecyl mercapto propyl diacid sulphate; sodium hexadecyl mercapto propyl di-acid sulphate; and sodiiun octadecyl mercapto propyl di-acid sulphate.

The new compounds covered in this case are useful generally wherever known wetting, detergent, and emulsifying agents have heretofore been used. They may be used by themselves or in combination with known wetting or detergent agents in those relations in which soap and soaplike products have previously been used. These compounds can be used in wool-washing or carbonizing baths. They are very useful in any textile treatment bath in which it is desirable to secure a thorough wetting of the textile material by the liquid of the treating bath. These compounds are useful addition agents to dye baths since they enable the dye to thoroughly wet the material to be dyed. They are also useful in 1eather-soaking, deliming and bating liquors.

They may be used as modifying agents in ore flotation processes and as emulsifiers for oils and bitumens. They may also be used to stabilize natural or synthetic emulsions or dispersions such as rubber latex, wax emulsions, and pharmaceutical emulsions. Another important application of these substances arises from their ability to inhibit the precipitation of ordinary soap in hard and acid waters. This property makes it possible to obtain a cheap detergent which is resistant to hard and acid waters by mixing small quantities of these substances with ordinary soap.

As many apparently widely different embodiments of this invention may be made without widely departing from the spirit and scope thereof, it is to be understood that the invention is 55 not limited to the specific embodiments thereof except as defined in the appended claims.

We claim: 1. New chemical compounds having the general formula 60 in which M stands for an alkali metal. a

2. A new chemical compound having the for- 65 mula 3. The process of making compounds having the general formula 75 M represents hydrogen or an alkali metal, which Cress aerate comprises sulphating compounds having the general formula AS--R(OH) 1 or 2.

4. The process of making compounds having the general formula in which A represents an alkyl group containing from twelve to eighteen carbon atoms, and M represents hydrogen or an alkali metal, which comprises sulphating compounds having the general formula A'S-'CH2CH2OH.

5. The process of making the compound having the formula which comprises stirring 10 parts of 2 hydroxyethyl cetyl sulphide, 7.5 parts of sodium pyrosulphate, and 2.7 parts of pyridine at 9095 C. until a sample dissolves in water to a clear foaming solution, stirring the reaction mixture into 40 parts of water, adding 10 parts of sodium chloride, completing the precipitation by stirring for several hours, and filtering. r

6. New chemical compounds having the general formula:

in which A represents an aliphatic group containing a chain of eight or more carbon atoms, R stands for an aliphatic hydrocarbon group, and M stands for hydrogen or a soluble salt-forming group.

'7. A process of making the compounds defined in claim 6 which comprises sulphating each hydroxyl group in the compounds having the general formula:

wherein A and R have the significance set forth in claim 6, by the use of an alkali metal pyrosulphate along with pyridine.

8. New chemical compounds having the general formula:

in which A represents an alkyl group containing a chain of from ten to thirty carbon atoms, R stands for a saturated aliphatic hydrocarbon group containing from two to six carbon atoms, and M stands for hydrogen or a soluble salt-forming group.

9. A process of making the compounds defined in claim 8 which comprises sulphating each hydroxyl group in the compounds having the general formula:

in which A represents an alkyl group containinga chain having from ten to thirty carbon atoms, and M stands for an alkali metal.

11. A process of making the compounds defined in claim 10 which comprises sulphating compounds having the general formula:

wherein A has the significance set forth in claim 10, by the use of an alkali metal pyrosulphate along with pyridine.

Search Pcccm 12. Sulphuric acid esters of compounds having wherein A represents an alkyl group containing the general formula: a straight chain of from ten to thirty carbon atoms. A S"CHZ CHOH 'CH2OH 14. An alkali metal salt of a sulphuric acid 5 wherein each hydroxyl group is esterified and ester ofacompound having the formula: 5

wherein A represents an allphatic group contalning a chain of eight or more carbon atoms.

13. Alkali metal salts of sulphuric acid esters wherein each hydroxyl group is esterified. of compounds having the general formula: 10 ALFRED WILLIAM BALDWIN. 10

A S CH2 CHOH CHZOH HENRY ALFRED PIGGOTT.

wherein each hydroxyl group is esterified and 

